JPH0768281B2 - Continuous production of cationized starch - Google Patents
Continuous production of cationized starchInfo
- Publication number
- JPH0768281B2 JPH0768281B2 JP1157052A JP15705289A JPH0768281B2 JP H0768281 B2 JPH0768281 B2 JP H0768281B2 JP 1157052 A JP1157052 A JP 1157052A JP 15705289 A JP15705289 A JP 15705289A JP H0768281 B2 JPH0768281 B2 JP H0768281B2
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- Prior art keywords
- starch
- substitution
- slurry
- reaction
- degree
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、カチオン化澱粉の連続的製造法に関するもの
であり、更に詳しくは澱粉を第４級アンモニウム塩と反
応させ、次に蒸煮して湖化せしめる製造法に関するもの
である。TECHNICAL FIELD The present invention relates to a continuous process for producing a cationized starch, more specifically, a starch is reacted with a quaternary ammonium salt and then cooked. The present invention relates to a lake producing method.
カチオン化澱粉は製紙業界において乾燥紙力増強剤，歩
留り向上剤，水性向上剤等に広く利用されている。Cationized starch is widely used in the paper manufacturing industry as a dry paper strength enhancer, a retention improver, a water improver and the like.
カチオン化澱粉は例えば以下に示す反応式によって合成
することができる。The cationized starch can be synthesized, for example, by the reaction formula shown below.
現在、市販のカチオン化澱粉は、主として非連続で長時
間を要するバッチ法で製造されている。この方法では40
〜50℃で10〜30時間反応させ、洗浄乾燥等の工程を経て
得た粉末カチオン化澱粉を水でスラリー化しクッカー
（蒸煮器）に送り糊液を得るものである。また連続法と
しては例えば特開昭57-164103号には、100℃以上，高い
pH,15％より高い澱粉濃度でカチオン化剤を加えたアル
カリ性澱粉を煮沸後、滞留時間30秒〜５分程度の反応帯
域に送る方法が記されている。また特開昭64-6001号に
は澱粉，カチオン化剤，水を含むスラリーをクッカーに
送り,2.5〜3kg/cm2の蒸気と接触させ加熱糊化澱粉と
し、次いで反応器に送り100〜110℃で２〜10分間の滞留
時間内でカチオン化剤と反応させる方法に使用される実
施装置についての記載がある。 At present, commercially available cationized starch is mainly manufactured by a batch method which is discontinuous and requires a long time. 40 this way
The reaction is carried out at -50 ° C for 10 to 30 hours, and the powdered cationized starch obtained through steps such as washing and drying is slurried with water and sent to a cooker (steamer) to obtain a paste solution. Further, as a continuous method, for example, in JP-A-57-164103, 100 ° C or higher
It describes a method of boiling alkaline starch to which a cationizing agent has been added at a starch concentration higher than pH 15%, and then sending it to a reaction zone having a residence time of about 30 seconds to 5 minutes. Further, in JP-A-64-6001, a slurry containing starch, a cationizing agent, and water is sent to a cooker, brought into contact with steam of 2.5 to 3 kg / cm 2 to make heated gelatinized starch, and then sent to a reactor for 100 to 110. There is a description of the equipment used for the method of reacting with a cationizing agent within a residence time of 2 to 10 minutes at ° C.
上記の方法は夫々、次のような問題点がある。すなわち
カチオン化剤を加えたアルカリ性澱粉を蒸煮後、反応機
に送る連続法は、カチオン化反応温度が高く、カチオン
化剤の加水分解が併発するうえに、滞留時間が長すぎる
ため一旦生成した結合が熱分解し、澱粉に対するカチオ
ン化剤の仕込量より期待される理論置換度に対して製品
置換度が低く、大略20〜40％のモル収率が得られるにす
ぎない。従って薬品コスト面で不利となり置換度の制御
範囲が狭くまた紙の増強性能面でも問題があった。また
澱粉が焦げ茶褐色に着色しやすい欠点もある。一方バッ
チ式による方法は比較的高い収率が得られるが、長時間
反応のため生産性に制限がある。Each of the above methods has the following problems. That is, the continuous method in which the alkaline starch to which the cationizing agent has been added is cooked and then sent to the reactor, the cationization reaction temperature is high, and the hydrolysis of the cationizing agent occurs concurrently. Is thermally decomposed and the product substitution degree is lower than the theoretical substitution degree expected from the charged amount of the cationizing agent to the starch, and only a molar yield of about 20 to 40% can be obtained. Therefore, it is disadvantageous in terms of chemical cost, the control range of the degree of substitution is narrow, and there is a problem in terms of the reinforcing performance of the paper. There is also a drawback that the starch tends to be dark brown and colored. On the other hand, the batch method gives a relatively high yield, but the productivity is limited due to the long reaction time.
本発明は上記の問題点を解決するためのものであって、
高反応収率で置換度の制御範囲の広い経済性に富むカチ
オン化澱粉の製法を提供することを目的とする。The present invention is for solving the above problems,
An object of the present invention is to provide a process for producing a cationized starch which has a high reaction yield and a wide control range of the degree of substitution and which is economically rich.
本発明はすなわち、第４級アンモニウム塩をアルカリ性
条件下で澱粉と反応させてカチオン化澱粉の糊液を得る
にあたり、 （Ａ）水性媒体中30〜50重量％の澱粉，下記一般式
（１）（２）で示される第４級アンモニウム塩の少なく
とも１種及びアルカリを30〜60℃において0.5時間以上
反応させる工程， （Ｂ）上記（Ａ）で生成したカチオン化澱粉のスラリー
を水で希釈し蒸煮して糊化せしめる工程 よりなることを特徴とするカチオン化澱粉の連続的製法
である。In the present invention, namely, when a quaternary ammonium salt is reacted with starch under alkaline conditions to obtain a paste solution of cationized starch, (A) 30 to 50% by weight of starch in an aqueous medium, the following general formula (1) (2) a step of reacting at least one kind of quaternary ammonium salt represented by (2) and an alkali at 30 to 60 ° C. for 0.5 hour or more, (B) diluting the slurry of the cationized starch produced in (A) above with water It is a continuous method for producing cationized starch, which comprises a step of steaming to gelatinize.
（但しR1〜R3は炭素数１〜４の低級アルキル基,Xはハロ
ゲン原子を示す） 通常エポキシプロピルトリアルキルアンモニウム塩又は
その前駆体となる３−ハロゲン−２ヒドロキシプロピル
トリアルキルアンモニウム塩が好ましく、例えばグリシ
ジルトリメチルアンモニウムクロライド（以下GTAとい
う）,3−クロロ−２−ヒドロキシプロピルトリメチルア
ンモニウムクロライド（以下CHAという）が有効に使用
される。 (However, R 1 to R 3 are lower alkyl groups having 1 to 4 carbon atoms, and X is a halogen atom.) Usually, an epoxypropyltrialkylammonium salt or a 3-halogen-2hydroxypropyltrialkylammonium salt which is a precursor thereof is Preferably, for example, glycidyl trimethyl ammonium chloride (hereinafter referred to as GTA) and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (hereinafter referred to as CHA) are effectively used.
本発明法を図面のプロセスフローにより説明する。スラ
リー調製槽（１）にはCHA（２）と苛性ソーダ水溶液
（３）とを予めスタティックミキサー（４）で混合した
水溶液が定量フィーダーにより供給され、また別に所定
量の澱粉（５）と水（６）が供給され撹拌機（１′）に
より撹拌される。CHAと苛性ソーダ水溶液とを別々に調
製槽へ供給すると、スラリーのpHが局部的に高くなり糊
化をひき起すので好ましくない。またCHAと苛性ソーダ
水溶液とをそのまま混合すると発熱が激しく分解の可能
性があるので希釈水（６′）を加えて混合するのが好ま
しい。液組成は澱粉濃度として30〜50重量％,CHA（60％
水溶液として）１〜４重量％，苛性ソーダ（48％水溶液
として）１〜４重量％が通常であるが、組成比を決定す
るには、まず澱粉に対してCHAの使用量（理論置換度）
を定め続いて水及び苛性ソーダの使用量を定める。この
場合、澱粉に対して苛性ソーダはできるだけ多く水はで
きるだけ少なくする方が収率の面で有利であるが、苛性
ソーダが多すぎると次の反応槽内で糊化し、また水が少
なすぎると撹拌，送液が困難となるので好ましくない。
澱粉濃度として30〜50重量％の範囲が適当である。例と
してコーンスターチにつき理論置換度が0.03の場合、重
量比で澱粉1.0に対しCHA0.052である。ここで水は1.0〜
2.3さらに好ましくは1.3〜1.8であり、苛性ソーダは0.0
3〜0.07,さらに好ましくは0.04〜0.05である。勿論、澱
粉の種類によっても異なる。The method of the present invention will be described with reference to the process flow of the drawings. An aqueous solution prepared by previously mixing CHA (2) and an aqueous solution of caustic soda (3) in a static mixer (4) was supplied to the slurry preparation tank (1) by a quantitative feeder, and a predetermined amount of starch (5) and water (6) were separately supplied. ) Is supplied and stirred by the stirrer (1 '). If CHA and the aqueous solution of caustic soda are separately supplied to the preparation tank, the pH of the slurry is locally increased and gelatinization is caused, which is not preferable. Further, if CHA and the caustic soda aqueous solution are mixed as they are, heat generation may occur violently and decomposition may occur. Therefore, it is preferable to add dilution water (6 ') and mix them. The liquid composition is such that the starch concentration is 30 to 50% by weight, CHA (60%
Normally, 1 to 4% by weight (as an aqueous solution) and 1 to 4% by weight of caustic soda (as a 48% aqueous solution) are used. To determine the composition ratio, first use the amount of CHA to starch (theoretical degree of substitution).
Then, determine the amount of water and caustic soda used. In this case, it is advantageous in terms of yield to use as much caustic soda as possible and less water as possible with respect to the starch, but if too much caustic soda is used, gelatinize in the next reaction tank, and if too little water is used for stirring, It is not preferable because it becomes difficult to transfer the liquid.
A suitable starch concentration range is 30 to 50% by weight. As an example, when the theoretical degree of substitution per corn starch is 0.03, the weight ratio is CHA 0.052 to 1.0 starch. Where water is 1.0
2.3 More preferably 1.3 to 1.8, and 0.03 for caustic soda.
It is 3 to 0.07, and more preferably 0.04 to 0.05. Of course, it also depends on the type of starch.
調製されたスラリーは、導管（F1）を通り反応槽（７）
に連続的に供給され槽底部より連続的に抜き出される。
（７′）は撹拌機，（７″）は加熱用ジャケットであ
る。平均滞留時間は長い程、反応収率はよいが、所要反
応槽容積も大となるので通常0.5〜６時間，好ましくは
1.5〜2.5時間で運転される。槽内の反応温度は高すぎる
と糊化し、低すぎると収率が低くなるので通常30〜60
℃，好ましくは40〜50℃で運転される。The prepared slurry passes through the conduit (F 1 ) and the reaction tank (7)
And is continuously withdrawn from the bottom of the tank.
(7 ') is a stirrer, and (7 ") is a heating jacket. The longer the average residence time is, the better the reaction yield is, but the required reaction tank volume is also large. Therefore, it is usually 0.5 to 6 hours, preferably
It will be operated in 1.5 to 2.5 hours. If the reaction temperature in the tank is too high, it will be gelatinized, and if it is too low, the yield will be low.
It is operated at ℃, preferably 40 to 50 ℃.
反応後のスラリーは、水（８）で希釈された後、導管
（F2）により蒸煮器（９）に送られる。希釈後の澱粉濃
度は高い程、操業能率は良いが、高すぎると蒸煮後の糊
が水に分散不能となるので通常５〜15重量％，好ましく
は８〜10重量％となるように希釈水量は調節される。The slurry after the reaction is diluted with water (8) and then sent to a steamer (9) through a conduit (F 2 ). The higher the starch concentration after dilution, the better the operating efficiency, but if it is too high, the paste after steaming will not be dispersible in water, so the amount of diluted water is usually 5 to 15% by weight, preferably 8 to 10% by weight. Is adjusted.
蒸煮工程では２〜4kg/cm2の蒸気（10）を直接接触させ
瞬間的に糊化される。蒸煮器（９）としては市販のクッ
カーを採用するのが好ましい。糊化温度は100〜120℃が
好ましく、滞留時間は糊化が不十分とならぬ限り、でき
るだけ短い方がよく通常30秒以内，長くとも１分以内で
運転される。蒸煮後の糊液は、通常２重量％濃度まで水
（11）で希釈され、導管（F3），製品貯槽（12）を経て
製紙工程に送られる。In the steaming process, 2 to 4 kg / cm 2 of steam (10) is directly contacted to instantly gelatinize. It is preferable to employ a commercially available cooker as the steam cooker (9). The gelatinization temperature is preferably 100 to 120 ° C., and the residence time is preferably as short as possible unless the gelatinization is insufficient, and the operation is usually within 30 seconds, and within 1 minute at the longest. The paste solution after boiling is usually diluted with water (11) to a concentration of 2% by weight, and sent to the papermaking process via the conduit (F 3 ) and the product storage tank (12).
以下、実施例及び比較例により本発明を説明する。なお
例中組成はいずれも重量単位である。Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. The compositions in the examples are all in weight units.
実施例１ 撹拌機を備えたステンレス製の80lスラリー調製槽
（１），撹拌機及び加熱用外部ジャケットを備えたステ
ンレス製の80l反応槽（７），及び内容積200mlの市販の
クッカー（９）を使用し第１図のように接続して、カチ
オン化澱粉の連続製造試験を行った。Example 1 A stainless steel 80 l slurry preparation tank (1) equipped with a stirrer, a stainless steel 80 l reaction tank (7) equipped with a stirrer and an outer jacket for heating, and a commercial cooker (9) with an internal volume of 200 ml. Was used and connected as shown in FIG. 1 to conduct a continuous production test of cationized starch.
スラリー調製槽における仕込液組成はコーンスターチ１
部，水1.4部（澱粉濃度41.7％）,60％CHA 0.052部,48％
NaOH 0.045部とした。理論置換度は0.0309である。定常
時においては、スラリー調製槽，反応槽共に内容量60kg
の液面が保たれており、F1部流量，F2部流量は共に30kg
/時であり反応槽の平均滞留時間は２時間，槽内温度は
約45℃であった。クッカーに入れる前の希釈水量は106k
g/時，クッカー出口温度107℃，クッカー内平均滞留時
間は６秒であった。The composition of the charged liquid in the slurry preparation tank is corn starch 1.
Part, water 1.4 parts (starch concentration 41.7%), 60% CHA 0.052 parts, 48%
The content was 0.045 parts of NaOH. The theoretical degree of substitution is 0.0309. At regular times, both the slurry preparation tank and reaction tank have an internal capacity of 60 kg.
The liquid level of is maintained, and the flow rate of the F 1 part and F 2 part are both 30 kg.
The average residence time in the reaction tank was 2 hours, and the temperature in the tank was about 45 ° C. The amount of dilution water before putting in the cooker is 106k
The cooker outlet temperature was 107 ° C, and the average residence time in the cooker was 6 seconds.
定常時における反応槽内のスラリー及びクッカー出口糊
液を採取し分析したところ以下の結果となった。The following results were obtained by collecting and analyzing the slurry in the reaction tank and the paste solution at the cooker outlet at regular times.
反応槽内スラリー…置換度0.0186,収率60.2％ クッカー出口糊液…置換度0.0167,収率54.0％ クッカー出口の糊液は僅かに黄色がかった透明液であっ
た。さらにクッカー出口に内容積11の反応管を接続し
高温滞留時間を長くする試験を行った。反応管内平均滞
留時間は4.8分，出口温度106〜107℃であった。出口に
おける糊液は茶褐色に着色しており、その分析結果は以
下のとおりである。Slurry in reaction tank: degree of substitution 0.0186, yield 60.2% Cooker outlet paste solution: degree of substitution 0.0167, yield 54.0% The paste solution at the cooker outlet was a slightly yellowish transparent liquid. Furthermore, a test was conducted to extend the high temperature residence time by connecting a reaction tube with an internal volume of 11 to the cooker outlet. The average residence time in the reaction tube was 4.8 minutes, and the outlet temperature was 106 to 107 ° C. The paste solution at the outlet is colored dark brown, and the analysis results are as follows.
反応管出口糊液…置換度0.0150,収率48.5％ 比較列１ 実施例１における反応槽を省略し、調製槽より直接クッ
カーに送液した。他の条件は全て実施例１と同様にして
運転を行った。定常時においての分析結果は以下のとお
りである。Reaction tube outlet paste solution: degree of substitution 0.0150, yield 48.5% Comparative column 1 The reaction tank in Example 1 was omitted, and the solution was directly fed from the preparation tank to the cooker. All other conditions were the same as in Example 1 for operation. The analysis results at regular times are as follows.
クッカー出口糊液…置換度0.0085,収率27.5％ 反応管 出口糊液…置換度0.0062,収率20.1％ 実施例２ 実施例１におけるF1部，F2部のスラリー供給速度を共に
15kg/時とし反応槽滞留時間を４時間とした場合の結果
は以下のとおりであった。Cooker outlet paste liquid… Substitution degree 0.0085, Yield 27.5% Reaction tube outlet paste liquid… Substitution degree 0.0062, Yield 20.1% Example 2 F 1 part and F 2 part slurry supply rates in Example 1 are both
The results were as follows when the reaction vessel residence time was 15 hours and the reaction vessel residence time was 4 hours.
反応槽内スラリー…置換度0.0212,収率68.6％ クッカー出口糊液…置換度0.0198,収率64.1％ 実施例３ 実施例２におけるCHAの仕込量を増加し理論置換度を向
上させた。仕込液組成は、コーンスターチ１部，水1.4
部,60％CHA 0.069部,48％NaOH 0.050部（理論置換度0.0
409）とし、他の条件は実施例２と同様にして運転し、
以下の結果を得た。Slurry in reaction tank: degree of substitution 0.0212, yield 68.6% Cooker outlet paste solution: degree of substitution 0.0198, yield 64.1% Example 3 The amount of CHA charged in Example 2 was increased to improve the theoretical degree of substitution. The composition of the charged liquid is 1 part of corn starch and 1.4 parts of water.
Part, 60% CHA 0.069 part, 48% NaOH 0.050 part (theoretical substitution degree 0.0
409) and other conditions were the same as in Example 2,
The following results were obtained.
反応槽内スラリー…置換度0.0294,収率71.9％ クッカー出口糊液…置換度0.0284,収率69.4％ 比較例２ 実施例３において澱粉濃度を小さくした。仕込液組成は
コーンスターチ１部，水4.95部（澱粉濃度17％）,60％C
HA 0.069部,48％NaOH 0.050部とし、他の条件は実施例
３と同様として運転し以下の結果を得た。Slurry in reaction tank: Substitution degree 0.0294, yield 71.9% Cooker outlet paste solution ... Substitution degree 0.0284, yield 69.4% Comparative Example 2 In Example 3, the starch concentration was reduced. The composition of the charged liquid is 1 part corn starch, 4.95 parts water (starch concentration 17%), 60% C
HA was 0.069 parts and 48% NaOH was 0.050 parts, and other conditions were the same as in Example 3 and operation was performed to obtain the following results.
反応槽内スラリー…置換度0.0182,収率44.5％ クッカー出口糊液…置換度0.0179,収率43.8％ 比較例３ 実施例３において反応槽滞留時間を短くした。F1部，F2
部におけるスラリー供給速度を共に180kg/時とし平均滞
留時間を20分とし他の条件は実施例３と同様として運転
し以下の結果を得た。Slurry in reaction tank: degree of substitution 0.0182, yield 44.5% Cooker outlet paste solution: degree of substitution 0.0179, yield 43.8% Comparative Example 3 In Example 3, the residence time in the reaction vessel was shortened. F 1 part, F 2
The slurry supply rate in each part was 180 kg / hour, the average residence time was 20 minutes, and the other conditions were the same as in Example 3, and the following results were obtained.
反応槽内スラリー…置換度0.010,収率26.9％ クッカー出口糊液…置換度0.0155,収率37.9％ 〔発明の作用，効果〕 本発明法の特徴は、製品置換度がスラリー反応の段階で
律せられることであり、同段階において理論置換度，ア
ルカリ使用量，槽内平均滞留時間，スラリー濃度の各因
子を適切に選択することにより極めて反応収率の良いカ
チオン化澱粉糊液が得られる。したがって薬品コストの
低減に有効であり、製品の紙力増強作用等の機能も優れ
ている。さらに上記の因子のうち、いずれかのものを操
作することにより製品置換度の調節が容易かつ広範囲に
可能である。Slurry in the reaction tank… Substitution degree 0.010, yield 26.9% Cooker outlet glue solution… Substitution degree 0.0155, yield 37.9% [Operation and effect of the invention] The feature of the present invention is that the product substitution degree is controlled at the stage of slurry reaction. Therefore, a cationized starch paste solution having a very good reaction yield can be obtained by appropriately selecting the factors such as the theoretical degree of substitution, the amount of alkali used, the average residence time in the tank, and the slurry concentration at the same stage. Therefore, it is effective in reducing the cost of chemicals, and also has excellent functions such as paper strengthening action. Further, by manipulating any one of the above factors, the degree of product substitution can be adjusted easily and in a wide range.
図面は本発明法を例示するプロセスフローシートであ
る。 （１）……スラリー調製槽，（４）……スタティックミ
キサー，（９）……蒸煮器（クッカー），（12）……製
品貯槽The drawing is a process flow sheet illustrating the method of the present invention. (1) …… Slurry preparation tank, (4) …… Static mixer, (9) …… Steamer (cooker), (12) …… Product storage tank
Claims (1)
で澱粉と反応させてカチオン化澱粉の糊液を得るにあた
り、 （Ａ）水性媒体中30〜50重量％の澱粉，下記一般式
（１）（２）で示される第４級アンモニウム塩の少なく
とも１種及びアルカリを30〜60℃において0.5時間以上
反応させる工程， （Ｂ）上記（Ａ）で生成したカチオン化澱粉のスラリー
を水で希釈し蒸煮して糊化せしめる工程 よりなることを特徴とするカチオン化澱粉の連続的製
法。 （但しR1〜R3は炭素数１〜４の低級アルキル基,Xはハロ
ゲン原子を示す）1. When a quaternary ammonium salt is reacted with starch under alkaline conditions to obtain a paste solution of cationized starch, (A) 30 to 50% by weight of starch in an aqueous medium, the following general formula (1) is used: (2) a step of reacting at least one kind of quaternary ammonium salt represented by (2) and an alkali at 30 to 60 ° C. for 0.5 hour or more, (B) diluting the slurry of the cationized starch produced in (A) above with water A continuous process for producing cationized starch, which comprises a step of boiling and gelatinizing. (However, R 1 to R 3 are lower alkyl groups having 1 to 4 carbon atoms, and X is a halogen atom.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1157052A JPH0768281B2 (en) | 1989-06-20 | 1989-06-20 | Continuous production of cationized starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1157052A JPH0768281B2 (en) | 1989-06-20 | 1989-06-20 | Continuous production of cationized starch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0321601A JPH0321601A (en) | 1991-01-30 |
| JPH0768281B2 true JPH0768281B2 (en) | 1995-07-26 |
Family
ID=15641150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1157052A Expired - Fee Related JPH0768281B2 (en) | 1989-06-20 | 1989-06-20 | Continuous production of cationized starch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768281B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827294A (en) * | 2012-09-21 | 2012-12-19 | 山东农业大学 | Method for producing cationic starch by using homogeneous phase drying method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI107160B (en) * | 1998-06-03 | 2001-06-15 | Raisio Chem Oy | Process for the preparation of highly cationic starch solutions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA980766A (en) * | 1972-03-31 | 1975-12-30 | Wadym Jarowenko | Process for preparing novel cationic flocculating agents and paper made therewith |
-
1989
- 1989-06-20 JP JP1157052A patent/JPH0768281B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827294A (en) * | 2012-09-21 | 2012-12-19 | 山东农业大学 | Method for producing cationic starch by using homogeneous phase drying method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0321601A (en) | 1991-01-30 |
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